Optical glass

ABSTRACT

An optical glass consisting essentially of a B 2  O 3  --La 2  O 3  --Gd 2  O 3  --WO 3  --ZrO 2  and/or Ta 2  O 5  system has high refractive and low dispersive characteristics with optical constants of 1.85-1.96 for Nd and 43-28 for νd, is free of poisonous ThO 2 , CdO and BeO ingredients, and suitable for mass production.

BACKGROUND OF THE INVENTION

This invention relates to an optical glass and, more particularly, to a high refractive and low dispersive optical glass having optical constants of 1.85 - 1.96 for Nd and 43-28 for νd and consisting of a B₂ O₃ --La₂ O₃ --Gd₂ O₃ --WO₃ --ZrO₂ and/or Ta₂ O₅ system which is free of poisonous oxides such as ThO₂, CdO and BeO and sufficiently stable to devitrification.

Various high refractive and low dispersive optical glasses containing the poisonous ingredients such as ThO₂, CdO and BeO have hitherto been reported and attempts have been made to improve these optical glasses and make them harmless to humans, as disclosed in British Pat. No. 1183996, Japanese Laid-open Patent Publication Nos. 37410/1973 and 55705/1974. These improved optical glasses, however, cannot achieve a high refractivity and a low dispersion observed in the optical glasses before the improvement was made. Further, optical glasses of higher optical properties have a greater tendency to devitrification and are not suitable for mass production.

SUMMARY OF THE INVENTION

It is, therefore, an object of the present invention to eliminate the above described disadvantages of the prior art optical glasses by providing a novel high refractive, low dispersive optical glass free of the poisonous oxides.

Concentrated studies and repeated experiments made by the inventors of the present invention have resulted in a finding that the above object can be attained and a high refractive and low dispersive optical glass of 1.85 - 1.96 for Nd and 43 - 28 for νd can be obtained by using an optical glass of a B₂ O₃ -- La₂ O₃ -- Gd₂ O₃ -- WO₃ -- ZrO₂ and/or Ta₂ O₅ system whose research data has hitherto been quite unknown.

According to the present invention, there is provided an optical glass containing a relatively small amount of B₂ O₃, a relatively large amount of La₂ O₃, an amount of a relatively wide range of Gd₂ O₃ and WO₃, a proper amount of ZrO₂ and/or Ta₂ O₅, and having the desired optical properties and stability. The optical glass according to the invention consists of a composition in weight percent of 10 to less than 17% B₂ O₃, 20 to 55% La₂ O₃, 0.5 to 38% Gd₂ O₃, 0.5 to 32% WO₃, 0 to 10% ZrO₂, 0 to 30% Ta₂ O₅, the total of said ZrO₂ and Ta₂ O₅ being 2 to 35%, 0 to 5.5% SiO₂, 0 to 5% GeO₂, 0 to 16% Y₂ O.sub. 3, 0 to 5% Tb₄ O₇, 0 to 38% Yb₂ O₃, the total of said Y₂ O₃, Tb₄ O₇ and Yb₂ O₃ being 0 to 40%, 0 to less than 2% TiO₂, 0 to 31% Nb₂ O₅, 0 to 3% SnO₂, 0 to 5% Al₂ O₃ 0 to 5% In₂ O₃, 0 to 5% Bi₂ O₃ and one or more oxides selected from the group consisting of MgO, CaO, SrO, BaO, ZnO and PbO, the amount of or the total amount of said MgO, CaO, SrO, BaO, ZnO and PbO being 0 to less than 2%.

DETAILED DESCRIPTION OF THE INVENTION

In the optical glass made according to the present invention, the above mentioned composition is selected for reasons stated below.

If the content of B₂ O₃ is less than 10%, a devitrification tendency considerably increases and mass production of the optical glass becomes difficult whereas if the content of B₂ O₃ exceeds 17%, the desired optical properties cannot be obtained.

La₂ O₃ is an essential ingredient for producing a high refractive and low dispersive optical glass and at least 20% of the La₂ O₃ content is required for satisfying the optical properties of the optical glass according to the present invention. If, however, the content of La₂ O₃ exceeds 55%, the devitrification tendency increases and a stable glass cannot be produced.

Gd₂ O₃ which provides the glass with optical properties similar to those provided by La₂ O₃ is necessary for preventing devitrification and maintaining stability required for achieving mass production of the optical glass. If the content of Gd₂ O₃ is less than 0.5%, such effects are reduced whereas if the content of Gd₂ O₃ exceeds 38%, phase separation occurs with a resulting difficulty in obtaining a homogeneous optical glass.

WO₃ is an important ingredient which has been found to be capable of being contained in a fairly wide content range for increasing the refractive index and preventing devitrification. If the content of WO₃ is less than 0.5%, such effects can scarcely be obtained whereas increasing the content of WO₃ above 32% increases tinting of the glass to an undesirable degree.

ZrO₂ contributes to preventing devitrification and is also effective for increasing the refractive index as compared with La₂ O₃. If, however, the content of ZrO₂ exceeds 10%, the devitrification tendency increases instead of decreases.

Ta₂ O₅ provides the glass with substantially the same refractive index as La₂ O₃ and, if the content of Ta₂ O₅ is up to 30%, it contributes to making an optical glass which is stable to devitrification. If the content of Ta₂ O₅ exceeds 30%, the quantity of insoluble matters in the melt increases resulting in difficulty in making a homogeneous optical glass.

In the optical glass made according to the present invention, introduction of ZrO₂ and/or Ta₂ O₅ as an ingredient is essential for preventing the devitrification tendency as well as maintaining the desired optical properties. If the sum of ZrO₂ and/or Ta₂ O₅ is less than 2%, sufficient effects of these ingredients cannot be expected whereas if the sum exceeds 35%, the glass becomes hard to melt and the tendency to devitrification increases.

Ingredients to be described below are not essential ingredients for the optical glass according to the invention but they are effective for correcting the optical properties of the glass and preventing the devitrification tendency further if they are used within their proper content ranges.

SiO₂ and GeO₂ are effective for increasing viscosity of the molten glass and thereby preventing devitrification. If the content of SiO₂ exceeds 5.5%, the quantity of insoluble matters in the melt increases resulting in difficulty in obtaining a homogeneous optical glass. If the content of GeO₂ increases above 5%, the devitrification tendency increases, instead of decreases so that a stable glass cannot be obtained.

Y₂ O₃, Tb₄ O₇ and Yb₂ O₃ are similar to La₂ O₃ in their effects on the optical glass made according to the present invention and are effective for preventing devitrification if the content of Y₂ O₃ is up to 16%, that of Tb₄ O₇ is up to 5% and that of Yb₂ O₃ is up to 38%, respectively. However, the devitrification tendency does not decrease, but on the contrary increases, if the contents of Y₂ O₃ and Yb₂ O₃ exceed the above mentioned amounts, so that a stable glass cannot be obtained. Increasing of the content of Tb₄ O₇ above the above mentioned amount is undesirable because the glass is tinted. Further, if the sum of the contents of Y₂ O₃, Tb₄ O₇ and Yb₂ O₃ exceeds 40%, the devitrification tendency increases and the glass is likely to become unstable.

TiO₂ and Nb₂ O₅ are effective for increasing the refractive index and preventing devitrification. If, however, the content of TiO₂ exceeds 2%, the glass is tinted to an undesirable degree. If the content of Nb₂ O₅ exceeds 31%, the devitrification tendency sharply increases.

SnO₂ is effective for preventing devitrification but increasing the content thereof above 3% increases tinting of the glass to an undesirable degree.

Al₂ O₃ is effective for increasing viscosity of the molten glass, preventing devitrification and preventing phase separation which occurs due to Gd₂ O₃. Increasing the content of Al₂ O₃ above 5%, however, increases the devitrification tendency.

In₂ O₃ and Bi₂ O₃ are effective for increasing the refractive index and preventing devitrification. If, however, the content of each of these ingredients exceeds 5%, tinting of the glass increases to an undesirable degree.

MgO, CaO, SrO, BaO, ZnO and PbO may effectively be used as melting agents for melting the SiO₂ material. If, however, the amount of or the total amount of one or more of these ingredients exceeds 2%, the devitrification tendency increases.

One or more of the above described oxide glass ingredients, e.g., Y₂ O₃, Al₂ O₃ and MgO, may be replaced, in part or in whole, with fluorides such as YF₃, AlF₃ and MgF₂ for further facilitating melting of the glass and preventing devitrification. The content of fluorine in the glass should preferably be held within a range not exceeding 2%.

Examples of the composition (in weight percent) of the optical glass according to the invention as well as optical properties (Nd, νd) and liquidus temperatures (° C) thereof are shown in Table 1. In these examples, the liquidus temperatures were obtained by maintaining a glass grain of about 1 mm in a temperature gradient furnace for 30 minutes and thereafter observing the glass sample.

As will be apparent from the Table, these examples of the optical glass all possess high refractive and low dispersive characteristics. Further, as will also be apparent from the liquidus temperatures in the Table, the optical glass is sufficiently stable to devitrification. Since these optical glasses contain a relatively small amount of B₂ O₃, they are higher in viscosity in melting than conventional optical glasses containing B₂ O₃ and La₂ O₃ and, accordingly, require a relatively high melting temperature (1340°-1420° C). These optical glasses, however, can be readily manufactured by melting the raw materials in a platinum crucible or the like, refining and stirring the melt to homogenize it and thereafter pouring it in a mould and annealing it.

                                      Table 1 - 1                                  __________________________________________________________________________     Components Weight Percent                                                                                                           Liquidus                  No.                                                                               B.sub.2 O.sub.3                                                                   La.sub.2 O.sub.3                                                                   Gd.sub.2 O.sub.3                                                                   WO.sub.3                                                                          ZrO.sub.2                                                                          Ta.sub.2 O.sub.5                                                                   SiO.sub.2                                                                         Y.sub.2 O.sub.3   Nd  νd                                                                             temperature                                                                    (° C)              __________________________________________________________________________     1  16.3                                                                              38.4                                                                               9.6 1.4                                                                               5.0 15.7                                                                               5.0                                                                                8.6              1.8538                                                                             42.6                                                                              1160                      2  11.0                                                                              38.0                                                                               3.0 13.5                                                                              4.5 15.0                                                                               3.0                                                                               12.0              1.9193                                                                             36.0                                                                              1200                      3  16.9                                                                              41.1                                                                               4.0 15.0                                                                              4.0 19.0                     1.8932                                                                             36.5                                                                              1150                      4  14.0                                                                              28.0                                                                               30.0                                                                               5.0                                                                               6.0 14.0                                                                               3.0                  1.9013                                                                             37.6                                                                              1160                      5  14.0                                                                              24.0                                                                               1.0 13.0                                                                              6.0 26.0   16.0              1.9178                                                                             30.1                                                                              1170                      6  15.0                                                                              55.0                                                                               0.5 5.0    24.5                     1.9083                                                                             35.4                                                                              1160                      7  10.5                                                                              25.0                                                                               26.0                                                                               30.0   6.0 2.5                  1.9128                                                                             34.1                                                                              1145                      8  16.0                                                                              39.0                                                                               1.0 14.0   30.0                     1.8894                                                                             31.0                                                                              1150                      9  15.0                                                                              30.0                                                                               20.0                                                                               0.5                                                                               7.0 27.5                     1.9147                                                                             34.8                                                                              1180                      10 10.0                                                                              34.5                                                                               15.0                                                                               15.0                                                                              4.0 17.0                                                                               4.5                  1.9166                                                                             36.0                                                                              1190                      11 14.0                                                                              40.0                                                                               1.0 10.0                                                                              7.0 28.0                     1.9218                                                                             30.5                                                                              1140                      12 16.0                                                                              20.0                                                                               38.0                                                                               5.0                                                                               6.0 15.0                     1.9103                                                                             37.4                                                                              1190                                                     Yb.sub.2 O.sub.3                                13 14.0                                                                              20.0                                                                               1.5 10.0                                                                              3.0 11.0                                                                               3.0   37.5           1.8802                                                                             36.1                                                                              1180                                                     Yb.sub.2 O.sub.3                                                                   Tb.sub.4 O.sub.7                            14 16.5                                                                              21.0                                                                               0.5 5.0                                                                               3.0 15.0   12.0                                                                              24.0                                                                               3.0        1.8945                                                                             37.0                                                                              1195                                                             Nb.sub.2 O.sub.5                        15 15.0                                                                              36.0                                                                               4.0 32.0                                                                              2.0     4.0           7.0    1.8633                                                                             32.1                                                                              1130                                                             Nb.sub.2 O.sub.5                                                                   YF.sub.3                            16 16.6                                                                              31.0                                                                               9.4 6.9                                                                               3.4 9.3 3.0                                                                               5.4        10.0                                                                               5.0                                                                               1.8843                                                                             29.1                                                                              1120                      __________________________________________________________________________

                                      Table 1 - 2                                  __________________________________________________________________________                                                          Liquidus                  No.                                                                               B.sub.2 O.sub.3                                                                   La.sub.2 O.sub.3                                                                   Gd.sub.2 O.sub.3                                                                   WO.sub.3                                                                          ZrO.sub.2                                                                          Ta.sub.2 O.sub.5                                                                   SiO.sub.2                                                                         Y.sub.2 O.sub.3   Nd  νd                                                                             temperature                                                                    (° C)              __________________________________________________________________________     17 13.0                                                                              41.5                                                                               1.5 20.0                                                                              3.5 17.0   2.0                                                                               TiO.sub.2      1.9402                                                                             33.2                                                        1.5                                                                                   Nb.sub.2 O.sub.5                         18 16.7                                                                              33.0                                                                               2.0 5.3                                                                               3.5 8.5              31.0    1.9582                                                                             28.0                                                                              1080                                                     GeO.sub.2                                                                          SnO.sub.2                                   19 12.0                                                                              31.0                                                                               6.0 25.0   18.0      5.0 3.0        1.9098                                                                             32.2                                                                              1085                                                            Al.sub.2 O.sub.3                         20 12.0                                                                              45.0                                                                               1.0 17.0                                                                              4.0 14.0                                                                               2.0          5.0     1.8720                                                                             36.4                                                                              1110                                                                In.sub.2 O.sub.3                     21 14.0                                                                              33.0                                                                               7.0 23.0                                                                              3.0 15.0                 5.0 1.9178                                                                             32.8                                                                              1080                                                     Bi.sub.2 O.sub.3                                22 14.0                                                                              34.0                                                                               5.0 21.0                                                                              4.0 17.0      5.0            1.9254                                                                             29.3                                                                              1045                                                         SrO                                         23 16.4                                                                              36.0                                                                               2.0 18.5                                                                              3.5 17.5                                                                               4.6       1.5        1.8502                                                                             31.2                                                                              1050                                                            MgF.sub.2                                24 15.3                                                                              40.0                                                                               2.0 17.5                                                                              3.0 16.2                                                                               3.8          2.2     1.8651                                                                             32.3                                                                              1080                      25 16.0                                                                              30.0                                                                               10.0                                                                               20.0                                                                              10.0                                                                               2.0 4.0                                                                               8.0               1.8666                                                                             34.9                         26 14.5                                                                              30.0                                                                               26.5                                                                               5.0                                                                               6.0 12.5                                                                               5.5                  1.8586                                                                             41.7                                                                              1150                                                     CaO                                             27 16.0                                                                              30.0                                                                               15.0                                                                               12.5                                                                              5.0 15.0                                                                               5.0   1.5            1.8571                                                                             35.5                                                            BaO                                         28 14.0                                                                              35.0                                                                               7.0 17.0                                                                              5.5 15.0                                                                               5.0       1.5        1.8727                                                                             32.7                                                                              1090                                                            ZnO                                      29 15.0                                                                              29.0                                                                               27.0                                                                               3.5                                                                               6.0 13.0                                                                               5.0          1.0     1.8591                                                                             41.8                                                                              1140                                                                PbO                                  30 12.1                                                                              39.0                                                                               4.0 14.5                                                                              6.0 15.5                                                                               3.0                                                                               4.0           1.9 1.9101                                                                             35.3                         31 13.5                                                                              32.0                                                                               27.0                                                                               4.5                                                                               5.0 14.0                                                                               4.0                  1.8811                                                                             40.9                         __________________________________________________________________________ 

What is claimed is:
 1. An optical glass consisting of a composition in weight percent of 10 to less than 17% B₂ O₃, 20 to 55% La₂ O₃, 0.5 to 38% Gd₂ O₃, 0.5 to 32% WO₃, 0 to 10% ZrO₂, 0 to 30% Ta₂ O₅, the total of said ZrO₂ and Ta₂ O₅ being 2 to 35%, 0 to 5.5% SiO₂, 0 to 5% GeO₂, 0 to 16% Y₂ O₃, 0 to 5% Tb₄ O₇, 0 to 38% Yb₂ O₃, the total of said Y₂ O₃, Tb₄ O₇, and Yb₂ O₃ being 0 to 40%, 0 to less than 2% TiO₂, 0 to 31% Nb₂ O.sub. 5, 0 to 3% SnO₂, 0 to 5% Al₂ O₃, 0 to 5% In₂ O₃, 0 to 5% Bi₂ O₃, and an oxide or oxides selected from the group consisting of MgO, CaO, SrO, BaO, ZnO and PbO, the amount of or the total amount of said MgO, CaO, SrO, BaO, ZnO and PbO being 0 to less than 2%.
 2. The optical glass according to claim 1 which includes a fluoride or fluorides in substitution, in part or in whole, for the oxide or oxides of the same element or elements as said fluoride or fluorides among the ingredients of said composition, the total amount of fluorine contained in said fluoride or fluorides being in a proportion of up to 2% by weight. 